Photographic sensitive material suitable for the silver-dyestuff bleaching method

ABSTRACT

wherein Z2 and Z3, which may be identical or different, each represents a non-metallic atomic grouping required for the completion of a benzothiazole or benzoselenazole ring, R3 represents a member selected from the second group consisting of a hydrogen atom, lower alkyl or aryl radical, R4 and R5 have the same meanings as R1 and R2 and at least one of said R4 and R5 is an alkyl radical containing a carboxyl or sulfo group, X represents an anion, m is 1 or 2, and m 1 if an intermolecular salt is formed.   wherein Z represents a non-metallic atomic grouping required for the completion of a naphthothiazole or naphthoselenazole ring, Z1 represents a non-metallic atomic grouping required for the completion of a naphthothiazole, benzothiazole, naphthoselenazole or benzoselenazole ring, R represents a member selected from the first group consistinf of a hydrogen atom, lower alkyl or aryl radical, R1 and R2 each represents an alkyl radical and at least one of said R1 and R2 is an alkyl radical containing a carboxyl or sulfo group, X represents an anion, n is 1 or 2, and n 1 if an intermolecular salt is formed: D R A W I N G A photographic sensitive material having at least one sensitive silver halide emulsion layer containing dyestuffs suitable for the silver-dyestuff bleaching method, the improvement which comprises a combination of at least one of sensitizing dyestuffs of the following general Formula (I) and at least one of sensitizing dyestuffs of the following general Formula (II):

United States Patent 1191 Shiba et al.

[ Nov. 18, 1975 PHOTOGRAPHIC SENSITIVE MATERIAL SUITABLE FOR THESILVER-DYESTUFF BLEACHING METHOD [75] Inventors: Keisuke Shiba; MasanaoHinata,

both of Minami-ashigara, Japan [73] Assignee: Fuji Photo Film Co., Ltd.,Japan [22] Filed: Nov. 2, 1973 [21] Appl. No.: 412,521

Related US. Application Data [63] Continuation of Ser. No. 184,585,Sept. 28, 1971,

abandoned.

[30] Foreign Application Priority Data Primary Examiner-J. Travis BrownAttorney, Agent, or F irmSughrue, Rothwell, Mion, Zinn & Macpeak [57]ABSTRACT 1 A photographic sensitive material having at least onesensitive silver halide emulsion layer containing dyestuffs suitable forthe silver-dyestuff bleaching method, the improvement which comprisesacombination of at least one of sensitizing dyestuffs of the followinggeneral Formula (I) and at least one of sensitizing dyestuffs of thefollowing general Formula (11):

wherein Z represents a non-metallic atomic grouping required for thecompletion of a naphthothiazole or naphthoselenazole ring, Z representsa non-metallic atomic grouping required for the completion of anaphthothiazole, benzothiazole, naphthoselenazole or benzoselenazolering, R represents a member selected from the first group consistinf ofa hydrogen atom, lower alkyl or aryl radical, R and R each represents analkyl radical and at least one of said R and R is an alkyl radicalcontaining a carboxyl or sulfo group, X represents an anion, n is 1 or2, and n=1 if an intermolecular salt is formed:

wherein Z and Z which may be identical or different, each represents anon-metallic atomic grouping required for the completionof abenzothiazole or benzoselenazole ring, R represents a member selectedfrom the second group consisting of a hydrogen atom, lower alkyl or arylradical, R and R have the same meanings as R, and R and at least one ofsaid R and R is an alkyl radical containing a carboxyl or sulfo group, Xrepresents an anion, m is l or 2, and m=l if an intermolecular salt isformed.

8 Claims, No Drawings PHOTOGRAPHIC SENSITIVE MATERIAL SUITABLE FOR THESILVER-DYESTUFF BLEACHING METHOD This is a continuation, of applicationSer. No. 184,585, filed Sept. 28, 1971, now abandoned.

FIELD OF THE INVENTION BACKGROUND OF THE INVENTION One of thedisadvantages in the silver-dyestuff bleaching method is that thesensitive rate of the dyed photographic layer is reduced to aconsiderable extent, The reason therefor is that the maximum sensitivewavelength is approximately identical to the maximum absorptionwavelength of dyestuff. The sensitivity rate of the sensitive layer inthe silver-dyestuff bleaching method is lower than that inother colorphotographic methods. Accordingly, a serious problem in thesilverdyestuff bleaching method is in the preparation of a layer havinga sufficient sensitivity.

In the art of manufacturing a silver halide emulsion, it has been wellknown that the addition of sensitizing dyestuffs to the emulsion spreadsthe sensitive spectrum region of the emulsion resulting in an opticallysensitized emulsion. The sensitizing dyestuffs used in the sensitivematerial for the silver-dyestuff bleaching method must satisfy somenecessary requirements.

Except for the high sensitization, sensitizing dyestuffs should notcause residual coloration afterithe photographic sensitive material istreated. Further, sensitizing dyestuffs must be adsorbed firmly ontosilver halide particles lest they must be substituted by dyestuffssuitable for the silver dyestuff bleaching method; otherwise thesensitizing effect is diminished highly by thepresence of dyestuffssuitable for the silver dyestuff bleaching method. 7

A multi-layer material contains at least a blue sensitive emulsionlayer, a green sensitive emulsion layer and a red sensitive emulsionlayer. It is necessary that each color sensitization region of these.three layers is :separated well, above all that the redsensitive'emulsion is as little green sensitive as possible. For thispurpose, a red sensitive layer having a low green sensitivity and a highred sensitivity-is required. The sensitizing dyestuff used in the redsensitive emulsion should not difdoes not show these characteristics.

An object of this invention is to provide a combination of sensitizingdyestuffs useful to the silver halide photographic emulsion used in thesilver-dyestuff bleaching method and, in particular, to provide aphotographic emulsion for the red sensitive layer, which has a highsensitivity and is substantially free from the residual coloration anddoes not provide the red sensitivity to other layers. Other objects willbe apparent to those skilled in the art as the description of thisinvention proceeds.

DESCRIPTION OF THE INVENTION Objects of this invention are accomplishedby using the combination of sensitizing dyestuffs represented by thefollowing general Formula (I) and (II):

wherein Z represents a non-metallic atomic grouping required for thecompletion of a naphthothiazole or naphthoselenazole ring, Z representsa non-metallic atomic grouping required for the completion ofnaphthothiazole, benzothiazole, naphthoselenazole or benzoselenazolering, R represents hydrogen atom, lower alkyl or aryl radical, R, and Reach represents alkyl radical such as, for example, methyl, ethyl,n-propyl, B-hydroxyethyl, ,B-acetoxyethyl and y-acetoxypropyl radical,alkyl containing carboxyl group (for example, carboxymethyl,B-carboxyethyl and 'y-carboxypropyl radical, 2-(2-carboxyethoxy)ethyl,alkyl containing sulfo group (for example, B-sulfoethyl, y-sulfopropyl,y-sulfobutyl, fi-sulfobutyl, Z-hydroxy-l-sulfopropyl, 2-acetoxy-l-sulfopropyl, 2-(3-sulfopropoxy)ethyl, 3- methoxy- 2-(3-sulfoprop oxy)propyl, 2-( 2-( 3-sulfopropoxy)ethoxy)ethyl and2-hydroxy-3-(3-sulfopropoxy)propyl radical) etc., and at least one of Rand R is an alkyl radical containing carboxyl or sulfo group, Xrepresents an anion, n is l or 2 and n =1 if an intermolecular salt isformed.

- quired for the completion of a benzothiazole or benzoselenazole ring,R represents a hydrogen atom, lower alkyl or aryl radical, R and R havethe same meanings as R and R and at least one of R and R represents analkyl radical containing a carboxyl or sulfo group, X represents ananion, m is l or 2 and m =l if an intermolecular salt is formed.

Examples of naphthothiazole and naphthoselenazole rings which may becompleted by Z and a-naphthothiazole, B-naphthothiazole, B,B-naphthothiazole, anaphthoselenazole, B-naphthoselenazole and [3,13-naphthoselenazole.

Examples of naphthothiazole, benzothiazole, naphthoselenezole andbenzoselenazole rings which may be completed by Z are(Ii-I'lfiPI'ItI'IOthIfiZOlG, B-naphthothiazole, B,/3-naphthothiazole,benzothiazole, 5- methylbenzothiazole, 5-chlorobenzothiazole, 5-methoxybenzothiazole, 5-bromobenzothiazole, 5 ,6- dimethylbenzothiazole,S-cyanobenzothiazole, 5- phenylbenzothiazole, 5-hydroxy-6-methylbenzo-Examples of R and R; as lower alkyl and aryl radicals are methyl, ethyl,n-propyl, phenyl, p-methoxyphenyl, o-carboxyphenyl and the like.

As examples of X, there may be mentioned chlorine, bromine, iodine,perchlorate, p-toluenesulfonic acid, ethyl sulfuric acid ion etc.

The sensitizing dyestuffs to be used in this invention are known tothose skilled in the art.

The combined use of sensitizing dyestuffs according to this inventionprovides a photographic emulsion having'a low green sensitivity and ahigh red sensitivity in the presence of dyestuffs suitable for thesilver dyestuff bleaching method. While, in the case of a red sensitivelayer.

Examples of sensitizing dyestuffs of the general Formula (I) used inthis invention are shown as follows, but

the sensitizing dyestuffs are not restricted only to these examples s H-\N (C 2 )a rf (CHQ SOI OCH lI-7 c 14,

(CH CH OMCHQ SOJ (CHQ SO I-I mula (I) to one of the Formula (II) used isnot critical but an especially effective range is 9:1 1:9 by weight andmay be varied according to the purpose for use.

The sensitizing dyestuffs of the general Formula (I) and (II) areintroduced together with the dyestuff suitable for the silver-dyestuffbleaching method into the photographic layer used to the method. It isconvenient to add the sensitizing dyestuffs to the emulsion, which hasbeen washed with water and is not used for coating, especially beforethe addition of the dyestuff suitable for the method.

The process for the addition of said sensitizing dyestuffs to thephotographic emulsion is well known in the field of manufacturing theemulsion. In general, it may be added as a solution in a solvent such aswater, methanol, ethanol, methyl cellosolve, etc., to the photographicemulsion.

For the emulsion used in this invention, silver halide such as silverchloride, bromide, iodobromide, chlorobromide and chloroiodobromide maybe used.

While a conventional gelatine-silver halide emulsion is used in thisinvention, resinous substances or cellulose derivatives which do noteffect adversely to the sensitive material, may be used instead ofgelatine.

The photographic emulsion used in this invention may containconventional additives such as chemical sensitizer, anti-fogging agent,stabilizer, hardener, coating assistant, plasticizer, developmentaccelerator and air anti-fogging agent.

The photographic emulsion may be coated in a common manner on a suitablesupporter such as glass, film of cellulose derivate, a film of syntheticresin, a laminated paper, a synthetic paper and Baryta paper.

The dyestuffs which are used together with the sensitizing dyestuffs andwhich are suitable for the silverdyestuff bleaching method are thosewhich are used commonly in the method. In particular, those containingphenolic hydroxyl group or sulfonic acid group are preferred. Preferreddyestuffs are described in th specification US. Pat. No. 3,157,508.

EXAMPLE 1 6 Single sensitizing dyestuffs and combined ones were addedrespectively to a silver iodobromide emulsion (iodine content: mol%) andstirred well for 20 minutes, and, after standing for a while, 19.0g/silver halide g mol of dyestuff of the following formula were addedand stirred well, both common coating assistant and hardener were addedand stirred well, and the whole h 5. Hardening for 5 min,

The ratio of sensitizing dyestuff of the general Forwas coated on acellulose triacetate basefThe treatment was carried out according to thefollowing formulation. The results are shown in the Table l.

1. Development for 5 min.

p-methylaminophenol hydrochloride l hydroquinone I 1 3 anhydrous sodiumsulfite potassium bromide I anhydrous sodium carbonate water enough tomake up I Washing with water for 5 min. Fixing for 5 min.

crystalline sodium thiosulfate potassium metabisulfite waterenough tomake up I l 4. Washing with water for 5min.

30% aq. solution of formaldehyde anhydrous sodium carbonate 2 g waterenough to make up I 6, Washing with water for 5 min. 7. Bleaching thedyestuff for l0 min.

thiourea 28 g potassium bromide 18 g Z-amino-3-hydroxyphenazine 3 gconc. hydrochloric acid 200 ml water enough to make up l l 8, Washingwith water for 5 min. 9, Bleaching-fixing for l0 min.

tetrasodium ethylenediaminetetracetate 26 g anhydrous sodium carbonate24 g ferric chloride l5 g anhydrous sodium sulfite 13 g crystallinesodium thiosulfate 200 g water enough to make up I 1 .IO. Washing withwater for 20 min.

The structural formula of dyestuff used was as follows:

What is claimed is: v

1. In a photographic sensitive material having at least one redsensitive silver halide emulsion layer contain ing cyan azo dyestuffssuitable for the silver-dyestuff bleaching method, theimprovement whichcomprises a combination of at least one of sensitizing dyestuffs'of thefollowing general Formula (I) and at least one of 2 sensitizingdyestuffs of the following general Formula (II):

R, r 1 c=ci-| c=cii "c r 1 R;1(X

wherein Z represents a non-metallic atomic grouping required for thecompletion of a naphthothiazole or naphthoselenazole ring, Z representsa non-metallic atomic grouping required for the completion of anaphthothiazole, benzothiazole, naphthoselenazole or benzoselenazolering, R represents a member selected from the first group consisting ofa hydrogen atom, lower alkyl or aryl radical, R and R each represents analkyl radical and at least one of said R and R is an alkyl radicalcontaining a carboxyl or sulfo group, X represents an anion, n is l or2, and n1 if an intermolecular salt is formed;

I Z a Z3 wherein Z and Z which may be identical or different, eachrepresents a non-metallic atomic grouping required for the completion ofa benzothiazole or benzoselenazole ring, R represents a member selectedfrom the second group consisting of a hydrogen atom, lower alkyl or arylradical, R and R having the same meanings as R, and R and at least oneof said R and R is an alkyl radical containing a carboxyl or sulfogroup, X represents an anion, m is 1 or 2, and m=l if an intermolecularsalt is formed.

2. The photographic sensitive material according to claim 1 wherein thesensitizing dyestuff according to.

Formula (I) is selected from the group consisting of the following:

3. The photographic sensitive material according to claim 1 wherein thesensitizing dyestuff according to Formula ll is selected from the groupconsisting of the (C Hg mom lected from the fourth group consisting ofmethyl, ethyl, n-propyl, ,B-hydroxyethyl, B-acetoxyethyl,yacetoxypropyl, carboxymethyl, B-carboxyethyl, y-carboxypropyl,2-(2-carboxyethoxy)ethyl, ,B-sulfoethyl, 'y-sulfopropyl, 'y-sulfobutyl,8-sulfobutyl, 2-hydroxy-lsulfopropyl, 2-acetoxy-l-sulfopropyl,2,(3-sulfopropoxy ethyl 3-methoxy-2-( 3-sulfopropoxy )propyl2-(2-(3-sulfopropoxy)eth0xy)ethyl and 2-hydroxy-3- (3 '-sulfop ropoxy)propyl.

6. The photographic sensitive material according to claim 1 wherein saidX is selected from the fifth group consisting of chlorine, bromine,iodine, perchlorate, p-toluenesulfonic acid, and ethyl sulfuric acid.

7. The photographic sensitive material according to claim 1 wherein saidZ is selected from the group consisting of a-naphthothiazole,B-naphthothiazole, 8,8- naphthothiazole, a-naphthoselenazole,B-naphthoselenazole, and B,B-naphthoselenazole.

8. The photographic sensitive material according to claim 1 wherein saidZ is selected from the group consisting of a-naphthothiazole,B-naphthothiazole, [3,8- naphthothiazole, benzothiazole,S-methylbenzothiazole, 5-chlorobenzothiazole, S-methoxybenzothiazole,5-bromobenzothiazole, 5,6-dimethylbenzothiazole, S-cyanobenzothiazole,S-phenylbenzothiazole, 5-hydroxy-6-methylbenzothiazole,S-hydroxybenzothiazole, 5-ethyoxy-6-methylbenzothiazole, 5-carboxybenzothiazole, a-naphthoselenazole, ,B-naphthoselenazole,B,B-naphthoselenazole, S-methylbenzoselenazole, 5-chlorobenzoselenazole,5-methoxybenzoselenazole, S-phenylbenzoselenazole,5,6-dimethylbenzolselenazole, S-hydroxybenzoselenazole.

1. IN A PHOTOGRAPHIC SENSITIVE MATERIAL HAVING AT LEAST ONE REDSENSITIVE SILVER HALIDE EMULSION LAYER CONTAINING CYAN AZO DYESTUFFSSUITABLE FOR THE SILVER-DYESTUFF BLEACHING METHOD, THE IMPROVEMENT WHICHCOMPRISES A COMBINATION OF AT LEAST ONE OF SENSITIZING DYESTUFFS OF THEFOLLOWING GENERAL FORMULA (1) AND AT LEAST ONE SENSITIZING DYESTUFFS OFTHE FOLLOWING GENERAL FORMULA (II):
 2. The photographic sensitivematerial according to claim 1 wherein the sensitizing dyestuff accordingto Formula (I) is selected from the group consisting of the following:3. The photographic sensitive material according to claim 1 wherein thesensitizing dyestuff according to Formula II is selected from the groupconsisting of the following:
 4. The photographic sensitive materialaccording to claim 1 wherein said first and second group members areselected from the third group consisting of methyl, ethyl, n-propyl,phenyl, p-methoxyphenyl, and O - carboxyphenyl.
 5. The photographicsensitive material according to claim 1 wherein said R1, R2, R3 and R4radicals are selected from the fourth group consisting of methyl, ethyl,n-propyl, Beta -hydroxyethyl, Beta -acetoxyethyl, gamma -acetoxypropyl,carboxymethyl, Beta -carboxyethyl, gamma -carboxypropyl,2-(2-carboxyethoxy)ethyl, Beta -sulfoethyl, gamma -sulfopropyl, gamma-sulfobutyl, delta -sulfobutyl, 2-hydroxy-1-sulfopropyl,2-acetoxy-1-sulfopropyl, 2,(3-sulfopropoxy)ethyl,3-methoxy-2-(3-sulfopropoxy)propyl, 2-(2-(3-sulfopropoxy)ethoxy)ethyland 2-hydroxy-3-(3''-sulfopropoxy)propyl.
 6. The photographic sensitivematerial according to claim 1 wherein said X is selected from the fifthgroup consisting of chlorine, bromine, iodine, perchlorate,p-toluenesulfonic acid, and ethyl sulfuric acid.
 7. The photographicsensitive material according to claim 1 wherein said Z is selected fromthe group consisting of Alpha -naphthothiazole Beta -naphthothiazole,Beta , Beta -naphthothiazole, Alpha -naphthoselenazole, Beta-naphthoselenazole, and Beta , Beta -naphthoselenazole.
 8. Thephotographic sensitive material according to claim 1 wherein said Z1 isselected from the group consisting of Alpha -naphthothiazole, Beta-naphthothiazole, Beta , Beta -naphthothiazole, benzotHiazole,5-methylbenzothiazole, 5-chlorobenzothiazole, 5-methoxybenzothiazole,5-bromobenzothiazole, 5,6-dimethylbenzothiazole, 5-cyanobenzothiazole,5-phenylbenzothiazole, 5-hydroxy-6-methylbenzothiazole,5-hydroxybenzothiazole, 5-ethyoxy-6-methylbenzothiazole,5-carboxybenzothiazole, Alpha -naphthoselenazole, Beta-naphthoselenazole, Beta , Beta -naphthoselenazole,5-methylbenzoselenazole, 5-chlorobenzoselenazole,5-methoxybenzoselenazole, 5-phenylbenzoselenazole,5,6-dimethylbenzolselenazole, 5-hydroxybenzoselenazole.